Method of coking carbonizable materials and of recovering vapors and gases resulting therefrom



Oct. 1., 1935- E. o. RHODES ET AL 2,016,051

METHOD OF COKING CARBONIZABLE MATERIALS AND OF RECOVERING VAPORS AND GASES RESULTING THEREFROM Filed Dec. 19, 1931 s Sheets-Sheet '1 I 1& J; ff

. L A i .6

g 4 5 w n :k .u: .cn: J9

8 29 I d 40 J5 R Q Q Q Q Q 4;; 1 2;

INIVENTORS mean-5' &

Oct. 1, 1935. 0 RHODES 11 AL 2,016,051

METHOD OF CCSKING CARBONIZABLE MATERIALS AND OF RECOVEBING VAPORS AND GASES RESULTING THEREFROM Filed Dec. 19, 1931 5 Sheets-Sheet 2 i: Y 1i l 15 q is I 25 .16 1 V l J1 "X? Oct. 1, 1935.

METHOD OF COKING E O. RHODES EIAL CAR BONIZABLE MATERIALS AND OF RECOVERING VAPORS AND GASES RESULTING THEREFROM Filed Dec. 19, 19:51 5 Sheets-Sheet 5 .46 5 a a l 7 f u Q J5 f@ +L 4 J1 J3 x v a a INVENTORJ fomu/va O. P/rodqs, & 060785 6'. Fiifigoafr/ck.

Patented Oct. 1, 1935 UNITED STATES PATENT OFFICE Edmund 0. Rhodes and James C. Fitzpatrick, Pittsburgh, Pa., assignors to American Tar Products Co. Inc., a corporation of Delaware Application December 19, 1931, Serial No. 582,008

Claims.

This invention relates to a process of manufacturing coke and gas, and more particularly to a method of operating coal-coking ovens to obtain suitable conditions for producing coke from liquid hydrocarbonaceous materials.

As is well known, great quantities of tar are produced from coal distillation plants, andthis tar is taken to near-by tar distillation plants for separation of various useful fractions. Pitch residues and tar oils are produced, and in manufacturing coke from these products, it has been the desire of operators to satisfactorily carry on the coking thereof in coal-coking ovens of the coal distillation plants.

It has been found difficult to produce coke efiiciently from liquid hydrocarbonaceous materials in coal-coking ovens, particularly of the type We have found that by means of our method of operation ovens ordinarily employed-for coal coking may be readily adapted to coking of liquid hydrocarbonaceous material. We have found also that in by-product coke-oven batteries comprising a plurality of oven chambers it has been made possible to convert a suiiicient number of coke-ovens of a battery or a plant from the use of coal to the use of liquid hydrocarbonaceous materials as the demand for coke from such materials increases and to return these ovens to the use of coal as the demand for coal coke increases or the demand for coke from hydrocarbonaceous materials,-such as pitch or tar, or oil, decreases.

The details of my invention will be described in connection with the accompanying drawings,

Figure 1 is a top plan view of a portion of a coke-oven battery adapted for operation in accordance with our invention;

Fig. 2 is a side elevational view, partly in crosssection, of the portion of the battery shown in Fig. 1;

Fig. 3 is a side elevational view, partly in crosssection, of a portion of the apparatus shown in Fig. 2, and

Fig. 4 is a top plan view of a portion of a cokeoven battery including certain modifications.

Referring to Figs. 1, 2 and 3, a coke-oven battery I may comprise coke-ovens of any suitable type, such as for example those shown and described in the patent of .Joseph Becker, No.

1,374,546. The battery I comprises a series of coke-oven chambers 2 of any desired number. Heating iiues 3 are provided between the oven chambers to heat the walls thereof by means of burning gases. Each of the oven chambers is 5 provided with charging openings 4, three or four being commonly provided for each oven chamber in the top thereof and kept closed during the coking operation.

Each oven is also provided with a gas off-take opening 5 Fig. 3 provided with an ascension pipe 6 connected to collecting mains l and 8 from which gases may be withdrawn at any point.

For charging the ovens with liquid hydrocarbonaceous material the later is pumped through suitable piping 9 to sprays III which are directed into the charging holes 4. The piping 9 may extend any distance along the top of the coke oven battery toisupply liquid hydrocarbonaceous material to any number of the oven chambers and may be arranged as shown in Fig. 4. The liquid hydrocarbonaceous material may be sprayed into the ovens alone or simultaneously with steam, or'gases, such as coke oven gas, producer gas or water gas, or mixtures of these.

Thai material to be coked may be introduced continuously or intermittently in any number of stages. The coking of the material is preferably carried on in the manner set forth in the H. Koppers Patent No. 1,715,240, and in the copending applications of E. O. Rhodes, Serial No. 338,644, flled Feb. 9,' 1929, issued as Patent No. 1,942,978; and Serial No. 500,540, filed Dec. 6, 1930, issued as Patent No. 1,942,980.

It has been found that after an oven has been used a number of times for the coking of liquid hydrocarbonaceous materials, conditions in the oven may be improved by charging it with coal and coking the coal. After pushing out the coalcoke the coking of the liquid hydrocarbonaceous 4o material in the oven may be resumed.

Ordinarily in coking pitch, or tar, or oil under certain conditions carbon collects on the walls. The coking chambers which are of highly refractory brick are generally cleaned by scraping or burning the collected carbon. This may cause the opening of cracks in the walls of an oven and/or spalling of the refractory lining.

In our process, a coking chamber may be used a number of times for pitch or tar or oil coking and then the coking chamber may be charged with coal and the coal coked therein. When coal coke is removed from a coking chamber there is left in the Joints and cracks of the brickwork of said coking chamber a deposit which prevents leakage, and surface conditions result which are favorable for pushing operations. After extensive pitch, tar or oil coking operations it is often found desirable to maintain or bring about normal surface conditions by charging the coking chamber with coal and coking the coal therein.

The system of collecting mains which we employ makes it possible to readily convert the ovens of a battery from the use 'of coal to the use of hydrocarbonaceousliquid material, or vice versa, and at the same time take care of the large volumes of vapors and gases evolved. As shown in Figs. 1, 2, and 3, each of the oven chambers may be connected to two collecting mains 'I and 8, as stated above. In Figs. 1 and 2, merely the first five ovens are shown connected to the main 8 as well as the main 1. The main 8 may, however, be extended any distance parallel with the main 1 so as to provide for connecting up any.

number of the ovens of the battery therewith.

In Fig. 3 is shown a type of ascension pipe 6 which may be used for connecting the coking chamber to the collecting mains. When coking hydrocarbonaceous liquid in an oven, the vapors and gases rise in the pipe 8, pass through a crossover pipe l3 and into the collecting main 8. A valve I4 is shown in open position and may be lowered to its seat l5 to prevent passage of vapors into the collecting main 8. The valve I4 is thus closed when converting an oven from the use of hydrocarbonaceous liquid to the use of coal.

While coking coal a valve l8 which is shown in closed position is raised from its seat H to permit the passage of coal gas intothe collecting main 1. When converting the coking chamber back to the use of hydrocarbonaceous liquid the valve I 6 is closed and the valve I4 again opened. We have shown the use of two collecting mains for the separate collection of vapors and gases from pitch for instance and from coal. If petroleum oil for instance, and pitch, and coal. are to be coked separately in a coke oven battery, three collecting mains may be used and vapors and gases from each may be collected separately. It has been found advantageous to collect the vapors and gases from these materials separately.

For the purpose of collecting vapors and gases in the collecting mains a cooling liquid is-sprayed into the mains, and condensates are flushed out thereby. Coal-gases are sprayed with water, tar, -or ammonia liquor and vapors and gases ob- The collecting main 1 which is used for 001- lecting vapors and gases from coal-coking ovens is provided with sprays l8 connected to a pipe l9 through which cooling liquid is fed, The collecting main 8 is also provided with sprays 20 which are connected to a feed pipe 2| through which cooling liquid is conducted to the sprays. Branch pipes 22 conduct cooling liquid to sprays 23, 24, and 25 which inject the liquid into the crossover pipe l3.

The condensates are permitted to flow out of the mains i and 8 at either end. Figs. 1. and 2 show means for withdrawing condensates from one end of the main 8 adjacent the end of the coke-oven battery I. The condensates from the main 1 may be withdrawn therefrom at the other end of the battery (not shown). The liquids in the main 8 are withdrawn through a pipe 26, the

open end 21 of which is connected to a trap 28 at a point slightly above the bottom thereof. A cover 29 is provided for an opening in the trap and solid matter may be withdrawn from time to time through the opening. 5

The liquids from the main 8 pass through the pipe 26 into a tank 30 in which they are permitted to settle. Various outlet pipes are provided for withdrawal of materials from tank 38 at different levels. When an aqueous cooling 10 liquid is employed, oily materials of low specific gravity are withdrawn through a pipe 3| and heavier materials are withdrawn through a pipe Fresh cooling liquid may be fed into the tank 30 25 through a pipe 39.

In cases where 011 is used as a flushing or cooling medium for a main connected to ovens in which pitch or oil are being coked, recirculation of the oil through the collecting main may be carried 30' on, and from time to time portions of the circulated oil may be withdrawn and sprayed into the coking chambers to be coked therein as set forth in an application of Charles J. Ramsburg, Serial No. 555,228, filed August 5, 1931, issued as Patent 35 No. 1,971,834.

Gases may be withdrawn separately from each of the mains 'l and 8 through pipes 40 and 4i,

' respectively. In some cases, as for instance, when coal-gas is collected in the main 1 and vapors and 40 gases from pitch are collected in the main 8, the ends of the mains may be connected by means of a pipe 42 provided with a valve 48. By this con nection gases from the main 8 may be conducted into the main 1 without danger of interfering with 45 the coal-coking ovens.

As shown in Fig. 4, collecting mains, such as 44 and 45 may extend along both sides of a coke-oven battery and may be connected to the various oven chambers by means of ascension pipes 48 and 41 50 respectively. Cooling liquid is fed to the mains 44 and 45 through pipes 48 and. 49, respectively, and distributed to the various sprays. The condensates pass out of the mains 44 and 45 through pipes 50 and 5 I, respectively, and the uncondensed 55 gases pass out through pipes 52 and 53, respectively.

One of the mains may be used for collecting vapors and gases from coal-coking ovens and the other for collecting vapors and gases from ovens in 60 which pitch or oil are being coked. Valves of wellknown structure, which are operated by levers 54 are provided in each of the ascension pipes so as to permit the passage of gases andvapors into one main.or the other, depending upon the material 65 being coked in an oven.

Hydrocarbonaceous liquid material to be coked is admitted to the pipe 9 from which it is distributed to the charging holes 4 through sprays It, as shown in Fig. 2. 70

As stated in the above mentioned applications of E. O. Rhodes, pitch, tar or oil may be'intro-1 duced into a coke-oven chamber at such a rate that the material settling in the chamber becomes substantially solid substantially as fast as it ac- The intermediate layer which is primarily 15 cumulates, or the pitch, tar or oil may be fed into an oven at such a rate that they are converted to a partially coked but yet plastic condition as fast as they are introduced. If pitch, tar or oil are fed in rapidly the charging may be done in stages and between each stage the material introduced may be heated in the oven until the rapid evolution of vapors has subsided.

Oil, pitch or tar may be satisfactorily introduced at the rate of 150 gals. per hour up to substantially 1200 or 1500 gals. per hour. ,The rate of feed depends upon the character of the hydrocarbonaceous liquid material to be coked, the temperature of the material charged, and the temperature of the carbonizing chamber. The length of the coking period depends upon the character of the hydrocarbonaceous material, the rate at which the material is charged, and the temperature of the carbonizing chamber.

For example, in coking a hard pitch, charging may be continued for a period of two to three hours and coking for a period of preferably five to eight hours. tar or oil, these periods may be extended. The temperature of an oven before charging may be about 1400 F. to 2200 F.

While hydrocarbonaceous liquid material is charged and coked, the collecting main into which the resulting gases and vapors are conducted is flushed with a cooling liquid. For example, for the purpose of cooling pitch vapors an intensive spray of water is fed into the main at a temperature of 150 to 195 F. at the rate of about 6000 gals. per oven per hour. The temperature of the gases entering a main from an oven in which pitch is being coked is around 1000 F. and they are cooled therein to around 199 F.

When coking heavy petroleum oils or petroleum cracking still residues, for instance, the collecting main may be flushed with a so-called bunker oil having a viscosity which varies up to 300 seconds at F., in accordance with the Saybolt-Furol test, and having a specific gravity of around 0.97.

Such an oil may be sprayed into the collecting main at the rate of substantially 1500 to 3000 gals. per hour per oven at a temperature of F.

After pitch-coke or oil-coke has been removed from an oven, the latter may be charged with coal in accordance with the usual practice. The coking of coal generally extends for a period of about 14 to 18 hours. The main into which the coal-gas is conducted is flushed with about 1000 gals. per oven per hour of water, tar or ammonia liquor.

In the ordinary'process of making coke from coal, it is not desirable or advantageous to condense the volatile constituents or the vapors directly at the ovens in the collecting mains, whereas in the production of coke from pitch or oil, it is desirable and essential that the vapors be condensed as soon as possible. A suflicient number of sprays are used in the mains connected to the pitch-coking and oil-coking ovens to convert the mains into condensers where substantially total condensation takes place.

The system provided by us is flexible and enables the production of coal coke, and of coke from hydrocarbonacequs liquid materials, in accordance with widely varying demands. This flexible operation is accomplished with the entire coke-oven plant continuously in operation even though the time for the cycle of operations differs for the different materials coked. The system requires a minimum outlay of capital for the installation, and the carrying charges for the Conditions being equal, in. coking relatively small additional equipment are very We claim as our invention:

1. In a method of operating a coke-oven battery to provide a flexible system of producing coke from coal and coke from liquid hydrocarbonaceous material in the oven chambers of the said battery, the steps comprising coking hydrocarbonaceous liquid material in at least one of the said chambers, pushing out the coke formed, and restoring a chamber previously employed for coking said hydrocarbonaceous liquid material to conditions more favorable for coking further quantities of hydrocarbonaceous liquid material by coking coal in said chamber and pushing the coal-coke out of said chamber.

2. In a method of operating a coke-oven battery to provide a flexible system of producing coke from coal and coke from liquid hydrocarbonaceous material in the oven chambers of the said battery, the steps comprising coking hydrocarbonaceous liquid material in at least one of said chambers, removing the coke formed, placing coal in a coking chamber previously employed for coking the said hydrocarbonaceous liquid material, coking the coal, and removing the coal-coke from the said chamber to restore it to conditions more favorable for coking further quantities of hydrocarbonaceous liquid material.

3. A method of operating a coke-oven battery to provide a flexible system of producing varying proportions of coke from coal and coke from liquid hydrocarbonaceous material in the oven chambers of the said battery, the said chambers being arranged side by side with heating fiues between them, which method comprises coking coal in some of said chambers of said battery while coking liquid hydrocarbonaceous material in other chambers of said battery and while heating the coal and the liquid hydrocarbonaceous material at their coking temperatures, restoring chambers previously employed for coking said liquid hydrocarbonaceous material to conditions more favorable for coking further quantities of liquid hydrocarbonaceous material by coking coal in saidtery for the production of coal coke and of coke a from hydrocarbon liquid material, the said cokeoven battery having a plurality of coking chambers arranged side by side and being of the type having refractory walls for said chambers with.

heating fiues therein and from which coke is discharged by a pushing operation, the steps comprising charging heavy hydrocarbon liquid material selected from a group consisting of oil, tar and pitch into at least one of said chambers of said battery, reducing the said hydrocarbon maing the coal, and pushing out the coke formed from said coal.

5. In a method of operating a coke-oven battery for the manufacture or coal coke and of coke from liquid hydrocarbonaceous material, said battery comprising a plurality of coking chambers and heating walls therefor, which chambers are provided with pipe connections to a plurality of collecting mains for vapors and gases, the steps comprising coking coal in some of said chambers and coking liquid hydrocarbonaceous material in other chambers of said battery, collecting hot gases, resulting from the coking 01' the coal, in one of said collecting mains and separately collecting hot gases, resulting from the coking of said liquid hydrocarbonaceous material, in another of said collecting mains; partially condensing the gases and vapors, resulting from the coking of the liquid hydrocarbonaceous material, in the collecting main therefor; and then con-' ducting the uncondensed gases and vapors from said latter collecting-maininto the said main for collecting hot gases and vapors resulting from 10 the coking of the coal.

- EDMUND O. RHODES.

JAMES C. FITZPATRICK. 

